Phenol-aldehyde condensation product.



STATES PATENT OFFICE.

ADRIAAN WILLEM cos 'rnn v n VOORHOUT, on THE HAGUE, NETHERLANDS.

PHENOL-ALDEHYDE CONDENSATION PRODUCT.

No Drawing.

To all whom it mag concern:

Be it known that I, ADRIAAN WILLEM Cosrnn VAN VooRrIoUT, subject of theQueen of the Netherlands, residing-at The Hague, Klngdom of theNetherlands, have invented new and useful Improvements in and Relatingto Phenol Aldehyde Condensation Products; and I dohereby declare thefollowing to be a full, clear, and exact description of thesame.

. This invention relates to phenol-aldehyde condensation products.

It is known, that phenol forms condensation products with formaldehyde,particularly if'catalysts or accelerators are present. It is also knownthat this reaction proceeds most smoothly and yields'thebest productswhen small quantities of alkaline catalysts are used. In this case thefirst condensation-product is an oily liquid, which becomes semi-solidas the reaction proceeds. If the reaction proceeds still farther, thisfirst condensation-product is converted into an infusible, insolubleproduct possessing great solidity and resistance to the action of most.chemicals.

Great difliculties had to be overcome in.

converting the mass into this latter modification. i When thecondensation into the desired final product is carried out attemperatures about 100 C. such temperatures being necessary in orderthat the reaction may proceed with a reasonable velocity, a large volumeof va ors are evolved, which cause the final pro uct to have a sponeagain a sponge-like structure isobtained' In order to prevent this,Baekeland has roposed to let the final condensation take-p ace underpressure and prefers this method to all others. (See the'above citedliterature). By this counterrpressure the evolution of vapors isprevented. and the mass hardens without foaming. It is thereforepossible .to work at higher temperatures1(110 to 140 Specification ofLetters Patent.

ing in a reflux con the counter-pressure from escaping from the finalproduct, this latter becomes more or less brittle. Also it is onlypossible to ob- Patented July 2, 1918.

Application filed December 22, 1916. Serial No. 138,377.

tain water-clear, transparent products with this method, if purecrystallized phenol is used and even then only if the thickness of theobject is relatively small, because the Water formed during the reactionremains in the mass and makes it turbid. When using the cresols insteadof phenol in this process, it is altogether impossible to obtain atransparent product.

The object of the invention is to overcome these drawbacks and so obtainon the one hand products which are much less brittle than the productsobtained according to Baekelands method and on the other hand to be ableto use also the cresols for obtaining water-clear, transparent odorlessproducts of any size.

The invention is based upon the following considerations If formaldehydereacts upon a phenol, e. 9., cresol,-water is formed. In order to obtaina quite homogeneous product, this water should be eliminated in onewayor other from the solidifying'mass. In addition to the water, formedduring the-reaction, there is also present the .water in which theformaldehyde and the alkaline catalyst are dissolved, and this alsoshould be ellminated. Furthermore it should be considered, that bycontinuous heating of the first condensation-product, in consequence. ofthe heatlib- I erated during condensation, there is a,.tendency of thewhole mass to solidify suddenly with violent foaming, giving a worthlessproduct. This may occur 6. g. when heatdenser, as described 1n theAmerican Patent 942809, page 2, lines Baekeland prevents this suddensolidifying in the first place bydiscontinu ng the heat-- ing. In thedescription of hls process he states that in aheated closed "vessel,which may be provided with a reflux condenser,

two layers are formed. The upper layer contains a little formaldehyde m'aqueous solution and the other layer the condensation product inwhichthe alkaline catlyst is dissolved. This first condensation product maybecome'more or less thick by continued hardenin mass,notwithstanding'the high undesirable qualitles 1n the final product. It

heating and is then converted into the final counter-pressurepreventsthe water, formed .by the condensation after the elimination ofthe solvent water, to evaporate out of the temperature (Baekelandmentions 120-200 C. and even higher); The water bubbles in thehardenedmass, making it opaque and. (as 'is evident) also brittle, which areboth allthe water, which has been used" as a,sol',

vent, has been evaporated and the condensa-v tion between formaldehydeand cresol proceeds, much heat is generatedwhich causes a heavy pressureof-the formaldehyde vapor.

. As already remarked the counter-pressure temperature rises to e g'.215 C. and the whole mass becomes so hard, that 1t 1s used byBaekelandprevents the escape of formaldehyde, but also makes itimpossible for the.water to escape in the form of steam or vapor out ofthe mass, which becomes very hard. The-evaporationof the solvent waterfor the formaldehyde and the alkaline" catalyzer is effected at ordinarypressure at temperatures of 100-105 0-. When this wa' 'ter is evaporated(about of the total:

quantity of cresol+formaldehyde solution' if equal parts of cresol orphenol and 40% formaldehyde-solution are taken) and heating iscontinued, a sudden condensation will take. place under foaming, duringwhich the only possible to take the'hardened massout of the vessel bythe use of a pinch bar.

According tothe present invention the first condensation-product is. notwholly freed from wa'ter'and is afterward'mixed with a liquid preventingtoo great arise of temperature; together with said'liquid it isconverted slowly at a comparatively low temperature, into the finalproduct.

The invention may be carried out in two I difi'erentways, one for makingtransparent water remains, in the final product and the. other formaking opaque products. As already observed the main ob ection againstcondensation under pressure, is that the mass brittle and opaque. It hasbeen proposed to avoid this drawback by adding 10% 'ofsodium-salicyla'te to the condensa-. jtion' product. This substance hasthe propcity of retaining water in solid solution. In

" this process however, it isabsolutely necesstrongly of phenol,whichcauses this process sary to dry below 80 C. in consequence of whichmore water remains in the final product and the time ofdryingbecomesextraordinarily long. The 'proluct so obtained istransparent. but very brittle and smells making able for all kinds ofobjects of ima e, a

obtained. The'process is carried out as fola. Process for themdnufactwre of transparent products.

In a vessel provided with a steam jacket and; a mechanical stirringdevice, .equal quantities of cresol which beforehand has been madetransparent and colorless by dis tillation or crystallization or purephenol and formaldehyde-solution (4.0%) are mixed together with 0.5%.solid potassium'hydroxid (t. e caustic alkali may, if desired, bedissolved "in. the cresol first, and then the formaldehyde'may be addedafterward). Steam is introduced into the steam jacket and undercontinual stirring the mass is heated and the water distilled ofl. Allof the solventwater )(about' 30% of the total charge) and half of theamount formed bythe reaction, calculated at about 14% .of the totalcharge is allowed to distil I The mass then begins to foam up strongly;the steam is shut off and twenty per cent. by volume'of ethylormethylalcohol is then added. This addition prevents .the condensationproceeding too 'qmekly. Half of the added alcohol-is dist1lled.olf,'then themass is cast into molds, the molds brought intodrying, chambers, through which a current of air is maintained, whichcarries with it the evolved vaof the. water, which is The temperature.in the drying.

ter (as well as the water already present as waterpformed by theproceeding condensa tlon) have both the opportunity of escaping free yout of the'molds, which are open. at

the top, and the final hardening only takes stances have evaporated. Theproducts are strong, in- .very suitart, 1m1ta-- fusible, insoluble,resistant an tion-amber and the like.

.6. Process for the manufacture of opaque exactly in the same way asdescribed under 136 a; however impure cresol or other phenol place whensubstantially all volatile sub-.

may be used now instead of alcohol, oil of turpentine in volume equal tofrom 1 to 4 per cent. of the mass, and 2 or 3% glycerin are added, whilealso a small per cent. of Vaseline or the like may be added. The castingintomolds and drying is effected as described under a, but thetemperature in the drying chambers must finally be raised to 180 C. Theproduct may be col0red by addin coloring mattersat the same tlme with te oil of turpentine, glycerin and vaseline. As colorin matters fuchsin,ruby red, deep-black (har -r'ubber imitation) methylblue, methyl-green,etc., may be used. In this rocess the sudden foaming is prevented by t eaddition of -oil of turpentine and glycerin. As however the mass hardenssooner a higher temperature is required to drive out the last traces ofWater. The Vaseline is added principally to facilitate the removing ofthe products out of the molds. As far as it does not exude, it makes themass opaque. v

No claim specific to this particular process per se is made in thepresent case, as such claims are incorporated in my companionapplication, Serial Number 213,389, filed J anuary 23, 1918.

What I claim is:

1. The process of producing phenol-aldehyde condensation products whichcomprises heating a mixture of equal parts of a phenol and a 40%solution of formaldehyde and not more than 0.5% of solid caustic alkali'until all the free Water originally present has been driven ofl", aswell as about one half the amount of Water formed in the condensationreaction, adding to the mixture a proportion of a liquid other thanwater and thereafter completing the reaction by heating the mass at acomparatively low temperature during a considerable period.

2. The process of producin phenol-aldehyde condensation products w ichcomprises heating a mixture of equal parts of a phenol and a 40%solution of formaldehyde and not more than 0.5% of solid caustic alkaliuntil all the free water originally present has been driven off, as wellas about one half the amount of water formed in the condensationreaction, adding to the mixture a proportion of a liquid other thanwater and thereafter completing the'reaction by heating the mass in acurrent of air at a temperature gradually risingfrom 60 C. to 180 C.

3. The process of producing phenol-aldehyde condensation products whichcomprises heating a mixture of equal parts of a phenol' and a 40%solution of formaldehyde and not more than 0.5% of solid caustic alkaliuntil all the free water originally present has been driven off, as wellas about one half the amount of water formed in the condensationreactiom'adding to the mixture a proportion of a liquid other than waterand thereafter completing the reaction by heating the mass in a currentof air at a temperature gradually rising during a period of 30 hoursfrom 60 C. to 180 C.

4. The process of producing phenol-aldehyde condensation products whichcomprises heating a mixture of equal parts of a phenol and a 40%solution of formaldehyde and not more than 0.5% of solid caustic alkaliuntil all the free water originally present has been driven off, as wellas about. one half the amount of water formed in the condensationreaction, adding to the mixture a quantity of alcohol equivalent to 20per cent..by volume of the original mass, and thereafter completing thereaction by heating the mass at a comparatively low temperature during aconsiderable period.

5. The process of producing phenol-aldehyde condensation products whichcomprises heating a mixture of equal parts of a phenol and a 40%solution of formaldehyde and not more than 0.5% of solid caustic alkaliuntil all the free water originally.

a phenol and a 40% solution of formaldehyde and not more than 0.5% ofsolid caustic alkali until all the free Water originally present hasbeen driven off, as well as about one half of the amount of water formedin the condensation reaction, adding to the mixture a quantity ofalcohol equivalent to 20 per cent. by volume of the original mass, andthereafter completing the re-.

action by heating the mass in a current ofair at a temperature graduallyrising during a period of 30 hours from 60 C. to 180 C.

7. The process of producing phenol-aldehyde condensation products whichcomprises heatinga mixture of equal parts of a phenol and a 40% solutionof formaldehyde and not more than 0.5% of solid caustic alkali until allthe free water originally present has beendriven ofl, as well as aboutone half the amount of water formed in the condensation reaction, addingto the mixture a quantity of alcohol equivalent to 20 per cent. byvolume of the original mass, evapcrating ofl" one half of the alcohol soadded and completing the reaction by heating the mass at a comparativelylow temperature during a considerable period.

8. The process of producing phenol-aldm 25, mlxture a quantity ofalcohol to the mixture a quantity of alcohol hyde condensation productswhich comprises heating a mixture of equal parts of a phenol'and a 40%solution offormaldehyde and not more than 0.5% of solid caustic alkaliuntil all the free water originally present has been driven off, aswellas about one half the amount of water formed in the condensationreaction, adding equivalent to 20 per cent. by volume of the originalmass, evaporating off one half of the alcohol and completing thereaction by heating the product in a current of air at a temperature atfirst below and later above the boiling point of water.

9. The process of producing phenol-aldehydecondensation products whichcomprises heating a mixture of equal flarts of a phenoland a 40%solution of formaldehyde and not more caustic alkali until all the freewater originally present has been driven off, as well as about one halfthe amount of water formed in the condensation reaction, adding to theequivalent to 20 percent. by volume of the original mass,

evaporating off one half of the alcohol and completing the reaction byheating the mass in a current of air at temperatures gradually r1singfrom 60 C. to 180 C.

10. The processof producing phenol-aldehyde condensation products whichcom-- prises heating a mixture of equal parts of a phenoland a 40%solution of formaldehyde and not more than 0.5% of I solid caust1calkali, until all the free water originally present has been driven oil,as well as about one half the amount of water formed in the condensationreaction, adding to the mixture a quantity of alcohol equivalent to 20per cent. by volume of the original mass, evaporating ofi one half ofthe alcohol and completing the reaction by heating the mass in a currentof air at a temone half of the alcohol and than 0.5% of solid ,twosubscribing witnesses.

perature gradually rising from 60 C. to

180 C. during a'period of 30 hours.

. 11. The process of producing phenol aldehyde condensation productswhich comprises heatin a mixture of equal parts of a phenol an a 40%solution of formaldehyde and not more than 0.5% of solid caustic alkaliuntil all the free water origi .nallypresent has been driven off, aswell as about one half the amount of Water alkali until all .the freewater originally present has been driven off, as well as'about one halfthe amount of water formed in the condensation reaction, stirring themixture during this heating process, adding to the mixture a quantity ofalcohol equivalent to 20 per cent. by volume of the original mass,evaporating off one half of the alcohol and completing the reaction byheating the mass in a current of air at a temperature gradually risingfrom 60 C. to 180 C.

during a period of 30 hours.

In testimony whereof, I have signed my name to this specification in thepresence of ADRIAAN WILLEM GOSTER VAN VOORHOUT.

' Witnesses:

ANsoN DU NADEGAALF, WILBUR J. CARR.

